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Crystals of the title racemic compound, C11H13NO2, consist of two types of mol­ecules (conformers); one mol­ecule has an exocyclic OH group in an equatorial position and the other has this group in an axial position. Consequently, the hydrogen-bond schemes for the two mol­ecules are different. The mol­ecules with equatorial OH groups create infinite parallel chains (formed by the same enantio­mer), connected by centrosymmetric dimers of mol­ecules (of mixed enantio­mers), both with axial OH groups. Possible inter­conversion of the conformers and the flexibility of the mol­ecule were studied by means of different MP2 and density functional theory (DFT) methods. The optimization of the structure by the DFT method confirmed the types of the hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106005178/sf1027sup1.cif
Contains datablocks IIb, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106005178/sf1027IIbsup2.hkl
Contains datablock I

CCDC reference: 605690

Comment top

Recently we have found that enantiomerically pure 2-hydroxy-2-methyl-1-tetralone, (I), can be used as a chiral auxiliary for the stereoselective synthesis and/or epimerization of α-amino acids (Solladié-Cavallo et al., 2002). We described the synthesis of (I) in racemic or enantiomerically enriched forms elsewhere (Solladié-Cavallo et al., 2001, 2002; Pažický et al., 2006). The (R)-2-hydroxy-2-methyl-1-tetralone enantiomer was prepared by a stereoselective oxidation with chiral oxazitidines in 95% ee (Davis & Weismiller, 1990). This method is efficient but rather costly, so we decided to attempt to prepare enantiomerically pure (I) via crystallization of its oxime (II). Such an enantioseparation method was successfully applied on a similar compound; enantiometrically pure 2-hydroxypinan-3-one was obtained via crystallization of its enantiomerically enriched oxime, followed by hydrolysis (Markowicz et al., 2002).

During the synthesis of the corresponding oxime from 2-hydroxy-2-methyl-1-tetralone, two racemic diastereoisomeric compounds, syn-(IIa) and anti-(IIb), were formed. Compound syn-(IIa) isomerized easily to the more stable anti-(IIb). By careful crystallization of (IIb), crystals suitable for X-ray structure analysis were prepared. The X-ray experiment revealed that oxime anti-(IIb) did not form a conglomerate but preferentially crystallized as a racemic compound. Therefore, the enantioseparation of anti-(IIb) is not possible starting from its racemic mixture.

The crystal structure and theoretical investigation of the electronic structure of the title racemic compound, (IIb), are presented here.

The numbering scheme for (IIb), together with the atomic displacement ellipsoids plot, is shown in Fig. 1. Selected geometric parameters are presented in Table 1. The two molecules in the asymmetric unit differ in the conformation of the six-membered ring, with a difference in the position of the exocyclic OH group. The molecules of type 1 (containing C11) have OH groups in axial positions, and the molecules of type 2 (containing C21) have OH groups in equatorial positions. From this point of view, the conformational flexibility of this ring is interesting. Although three atoms in this ring formally have sp2-hybridization and further restraint is imposed by conjugation of the N—OH bond with the aromatic ring, the molecule is still quite flexible. Calculations at the MP2/6–31+G** (Pople et al., 1976; Frisch et al., 1990; Fletcher et al., 1999; Hehre et al., 1972; Clark et al., 1983) and B3LYP/6–31+G** (Becke, 1988, 1992a,b, 1993; Lee et al., 1988) levels showed that a conformational change between the OH-equatorial and OH-axial configurations is possible (Table 2) with an intermediate skew conformation, as seen in Figs. 2 and 3. A l l combinations of the standard quantum chemical methods and the basis sets used agree with the fact that the saturated ring is quite flexible and with the ordering of all three conformers discussed.

The two molecules in the asymmetric unit have different hydrogen-bonding schemes (Fig. 4). The molecules of type 2, with OH in the equatorial position, form infinite chains in the a direction. These chains are connected by centrosymmetric dimers formed by molecules of type 1. The dimers are formed in a manner similar to those for, for example, (±)dibenzobicyclo[b,f][3.3.1]nona-5a,6a-dien-6,12-dioxime (Field et al., 2002; Levkin et al., 2003), (E)-17-oximino-3-hydroxy-1,3,5(10)-estratriene (Hejaz et al., 1999) and 17α-benzyl-16-hydroxyimino-3-methoxyestra-1,3,5(10)-trien-17β-ol (Stanković et al., 1996). The hydrogen–bonding geometries for (IIb) are compared in Table 3. The theoretical investigation of hydrogen bonds was performed using the Vienna ab-initio simulation package VASP (Kresse & Furthmüller, 1996). The calculations were based on the DFT with periodic boundary conditions (Jones & Gunnarsson, 1989) using generalized gradient approximation (GGA) in exchange-correlation functional. The optimization of the structure by the DFT method was performed mainly to improve the positions of the H atoms. The calculations confirmed the types of the hydrogen bonds found by the experiment and refined their bond lengths.

The hydrogen-bonding pattern can be described using graph-set theory (Bernstein et al., 1995; Grell et al., 1999). The first-level graph-set descriptors are dimers D(2) and D(2), a ring R22(6), and a string S(5) for strong hydrogen bonds ad, respectively, while the second-level descriptors are assigned as C22(8) for bonds a and b, D33(14) for bonds a and c, and D33(12) for bonds b and c. The assignment of graph-set descriptors was performed using PLUTO, as described by Motherwell et al. (1999), and the notation of the hydrogen bonds here is that given in Table 3 and Fig. 4.

Experimental top

An ethanol/water solution of an equimolar ratio of racemic 2-hydroxy-2-methyl-1-tetralone, (I), hydroxylamine hydrochloride (NH2OH·HCl) and sodium acetate (AcONa) was stirred for 6 d at room temperature, whereupon a mixture of diastereoisomers (IIa) and (IIb) was formed. The pure diastereoisomer (IIb) was obtained by flash chromatography on SiO2, followed by crystallization. To a mixture of II(b) (36 mg 188.3 mmol) and hexsol (5.4 ml, light fraction of petrol ether), toluene (1.2 ml) was added. The mixture was heated to reflux. The solution obtained was left to stand in a cotton-covered flask in a small Dewar flask overnight. Straw-like crystals (32 mg, 167.3 mmol) were obtained in 88.9% yield, m.p. 387–389 K. Recrystallization was performed from a warm solution of II(b) (28 mg, 146.4 mmol) in hexsol (6.0 ml) and toluene (1.5 ml), standing in a cotton-covered flask in a small Dewar flask at room temperature. After 24 h, the solution was seeded with one microscope-selected crystal. In this manner, X-ray quality crystals were obtained after 48 h. The crystals were filtered off, washed with hexsol and dried in air (yield 10.9 mg, 57.0 mmol, 38.9%).

Refinement top

C-bound H atoms for compound (IIb) were constrained to the ideal geometry using an appropriate riding model and were refined isotropically with common displacement parameters for respective groups. The C—H distances were kept fixed at 0.95 Å for aromatic H atoms and at 0.99 Å for secondary H atoms. For methyl groups, the C—H distances (0.98 Å) and C—C—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with the starting position based on the threefold averaged circular Fourier synthesis. For the hydroxy groups, the O—H distance (0.84 Å) and C—O—H angle (109.5°) were used for calculating a starting position based on the circular Fourier synthesis; both the torsion angle and the O—H distance were then allowed to refine.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995) and SADABS (Sheldrick, 2002); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A perspective drawing showing the atom-numbering scheme of (IIb). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A schematic representation of the relative energies of the conformations of (IIb) and transition states connecting them.
[Figure 3] Fig. 3. A schematic representation of the skew conformation of (IIb).
[Figure 4] Fig. 4. The hydrogen-bonding pattern in the crystal structure of (IIb). H atoms not involved in strong hydrogen bonds have been omitted for clarity. For symmetry codes and notation of hydrogen bonds see Table 3.
anti-2-Hydroxy-2-methyl-1-tetralone oxime top
Crystal data top
C11H13NO2Z = 4
Mr = 191.22F(000) = 408
Triclinic, P1Dx = 1.283 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.3655 (2) ÅCell parameters from 3464 reflections
b = 9.6851 (2) Åθ = 2.2–25.5°
c = 14.4720 (1) ŵ = 0.09 mm1
α = 93.375 (1)°T = 173 K
β = 99.476 (1)°Plate, colourless
γ = 102.288 (1)°0.46 × 0.11 × 0.01 mm
V = 990.22 (3) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer
3654 independent reflections
Radiation source: fine-focus sealed tube2215 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
ω scansθmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 88
Tmin = 0.960, Tmax = 0.999k = 1111
11309 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0551P)2]
where P = (Fo2 + 2Fc2)/3
3654 reflections(Δ/σ)max < 0.001
266 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C11H13NO2γ = 102.288 (1)°
Mr = 191.22V = 990.22 (3) Å3
Triclinic, P1Z = 4
a = 7.3655 (2) ÅMo Kα radiation
b = 9.6851 (2) ŵ = 0.09 mm1
c = 14.4720 (1) ÅT = 173 K
α = 93.375 (1)°0.46 × 0.11 × 0.01 mm
β = 99.476 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3654 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
2215 reflections with I > 2σ(I)
Tmin = 0.960, Tmax = 0.999Rint = 0.068
11309 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.121H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.18 e Å3
3654 reflectionsΔρmin = 0.22 e Å3
266 parameters
Special details top

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equiped with a LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 3464 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O110.3489 (2)0.75256 (16)0.18986 (10)0.0241 (4)
H110.238 (4)0.7465 (14)0.2117 (16)0.045 (2)*
O120.0373 (2)0.87794 (18)0.06966 (10)0.0301 (4)
H120.041 (3)0.936 (3)0.0787 (7)0.045 (2)*
O210.0573 (3)0.7526 (2)0.28386 (11)0.0375 (5)
H210.048 (4)0.756 (3)0.2598 (9)0.045 (2)*
O220.4307 (2)0.7460 (2)0.35495 (11)0.0364 (5)
H220.511 (3)0.748 (3)0.3003 (16)0.045 (2)*
N110.1423 (3)0.9074 (2)0.02217 (12)0.0246 (5)
N210.2541 (3)0.7382 (2)0.33542 (13)0.0273 (5)
C110.3873 (3)0.8794 (2)0.14159 (15)0.0224 (5)
C120.5965 (3)0.9124 (2)0.13849 (16)0.0260 (6)
H12A0.66900.93400.20360.036 (2)*
H12B0.62770.99800.10490.036 (2)*
C130.6564 (3)0.7913 (3)0.09017 (16)0.0281 (6)
H13A0.78470.82650.07660.036 (2)*
H13B0.66340.71680.13380.036 (2)*
C140.5262 (3)0.7263 (2)0.00020 (15)0.0244 (6)
C150.3416 (3)0.7438 (2)0.02187 (15)0.0236 (6)
C160.2770 (3)0.8420 (2)0.04107 (15)0.0220 (5)
C170.5921 (4)0.6411 (3)0.06167 (17)0.0340 (6)
H170.71900.63120.04740.045 (3)*
C180.4779 (4)0.5717 (3)0.14241 (18)0.0414 (7)
H180.52570.51540.18430.045 (3)*
C190.2933 (4)0.5838 (3)0.16252 (18)0.0442 (8)
H190.21250.53380.21770.045 (3)*
C1100.2249 (4)0.6680 (3)0.10315 (17)0.0374 (7)
H1100.09670.67470.11750.045 (3)*
C1110.3396 (4)1.0023 (3)0.19507 (16)0.0299 (6)
H11A0.20510.97930.19890.045 (2)*
H11B0.36781.08780.16220.045 (2)*
H11C0.41531.01930.25870.045 (2)*
C210.0653 (3)0.7416 (3)0.38287 (16)0.0260 (6)
C220.2028 (4)0.8707 (3)0.43698 (18)0.0358 (7)
H22A0.32940.87590.42080.036 (2)*
H22B0.16120.95750.41870.036 (2)*
C230.2152 (4)0.8641 (3)0.54285 (18)0.0406 (7)
H23A0.30380.80390.56450.036 (2)*
H23B0.26910.96090.57480.036 (2)*
C240.0292 (4)0.8066 (3)0.57317 (17)0.0327 (6)
C250.1370 (3)0.7500 (2)0.50857 (15)0.0254 (6)
C260.1258 (3)0.7414 (2)0.40720 (15)0.0236 (5)
C270.0222 (4)0.8073 (3)0.66868 (18)0.0417 (7)
H270.13430.84520.71340.045 (3)*
C280.1427 (4)0.7546 (3)0.69970 (18)0.0435 (8)
H280.14390.75540.76530.045 (3)*
C290.3069 (4)0.7003 (3)0.63567 (17)0.0381 (7)
H290.42160.66470.65700.045 (3)*
C2100.3042 (4)0.6979 (3)0.54069 (16)0.0310 (6)
H2100.41750.66040.49670.045 (3)*
C2110.1253 (3)0.6042 (2)0.40441 (17)0.0321 (6)
H21A0.03180.52360.36840.045 (2)*
H21B0.13370.59380.47180.045 (2)*
H21C0.24890.60680.38690.045 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0223 (10)0.0296 (9)0.0219 (9)0.0061 (8)0.0058 (7)0.0081 (7)
O120.0290 (10)0.0392 (10)0.0209 (9)0.0115 (8)0.0042 (7)0.0031 (7)
O210.0265 (11)0.0605 (12)0.0302 (10)0.0137 (10)0.0111 (8)0.0127 (9)
O220.0181 (10)0.0704 (13)0.0235 (9)0.0153 (9)0.0030 (8)0.0106 (9)
N110.0239 (12)0.0309 (11)0.0170 (10)0.0033 (10)0.0003 (9)0.0064 (8)
N210.0167 (11)0.0408 (13)0.0261 (11)0.0080 (10)0.0054 (9)0.0062 (9)
C110.0245 (14)0.0242 (13)0.0195 (12)0.0054 (11)0.0049 (10)0.0075 (10)
C120.0242 (14)0.0287 (13)0.0229 (13)0.0013 (11)0.0032 (11)0.0055 (10)
C130.0222 (14)0.0329 (14)0.0315 (14)0.0062 (12)0.0098 (11)0.0083 (11)
C140.0301 (15)0.0243 (13)0.0222 (13)0.0078 (11)0.0104 (11)0.0068 (10)
C150.0311 (15)0.0221 (13)0.0181 (12)0.0052 (11)0.0054 (10)0.0061 (10)
C160.0197 (13)0.0243 (13)0.0215 (12)0.0018 (11)0.0048 (10)0.0073 (10)
C170.0384 (17)0.0311 (15)0.0392 (16)0.0111 (13)0.0188 (13)0.0113 (12)
C180.069 (2)0.0326 (16)0.0302 (15)0.0188 (16)0.0195 (15)0.0029 (12)
C190.067 (2)0.0363 (16)0.0254 (15)0.0157 (15)0.0038 (14)0.0052 (12)
C1100.0480 (18)0.0327 (15)0.0298 (15)0.0130 (14)0.0018 (13)0.0001 (12)
C1110.0332 (16)0.0347 (14)0.0224 (13)0.0112 (12)0.0024 (11)0.0025 (11)
C210.0203 (14)0.0325 (14)0.0267 (13)0.0062 (11)0.0071 (10)0.0062 (11)
C220.0238 (15)0.0314 (15)0.0511 (17)0.0032 (12)0.0077 (13)0.0045 (13)
C230.0322 (17)0.0352 (16)0.0469 (17)0.0044 (13)0.0055 (13)0.0076 (13)
C240.0347 (16)0.0318 (15)0.0297 (15)0.0135 (13)0.0038 (12)0.0054 (11)
C250.0277 (15)0.0296 (14)0.0196 (13)0.0118 (12)0.0006 (11)0.0009 (10)
C260.0247 (14)0.0237 (13)0.0218 (13)0.0048 (11)0.0032 (11)0.0030 (10)
C270.050 (2)0.0426 (17)0.0271 (15)0.0177 (15)0.0143 (14)0.0101 (12)
C280.065 (2)0.0530 (18)0.0188 (14)0.0318 (17)0.0034 (15)0.0008 (13)
C290.0428 (18)0.0529 (17)0.0275 (15)0.0246 (15)0.0126 (13)0.0085 (13)
C2100.0280 (16)0.0470 (16)0.0212 (13)0.0156 (13)0.0041 (11)0.0055 (11)
C2110.0257 (15)0.0347 (15)0.0377 (15)0.0084 (12)0.0095 (12)0.0022 (12)
Geometric parameters (Å, º) top
O11—C111.448 (2)C19—H190.9500
O11—H110.9120C110—H1100.9500
O12—N111.403 (2)C111—H11A0.9800
O12—H120.8936C111—H11B0.9800
O21—C211.436 (3)C111—H11C0.9800
O21—H210.8041C21—C261.506 (3)
O22—N211.392 (2)C21—C2111.521 (3)
O22—H220.9095C21—C221.512 (3)
N11—C161.288 (3)C22—C231.526 (4)
N21—C261.278 (3)C22—H22A0.9900
C11—C121.515 (3)C22—H22B0.9900
C11—C161.527 (3)C23—C241.510 (4)
C11—C1111.516 (3)C23—H23A0.9900
C12—C131.512 (3)C23—H23B0.9900
C12—H12A0.9900C24—C251.397 (3)
C12—H12B0.9900C24—C271.391 (4)
C13—C141.499 (3)C25—C2101.392 (3)
C13—H13A0.9900C25—C261.481 (3)
C13—H13B0.9900C27—C281.372 (4)
C14—C171.394 (3)C27—H270.9500
C14—C151.393 (3)C28—C291.379 (4)
C15—C1101.400 (3)C28—H280.9500
C15—C161.481 (3)C29—C2101.377 (3)
C17—C181.367 (4)C29—H290.9500
C17—H170.9500C210—H2100.9500
C18—C191.374 (4)C211—H21A0.9800
C18—H180.9500C211—H21B0.9800
C19—C1101.375 (3)C211—H21C0.9800
C11—O11—H11109.5C11—C111—H11C109.5
N11—O12—H12109.5H11A—C111—H11C109.5
C21—O21—H21109.5H11B—C111—H11C109.5
N21—O22—H22109.5O21—C21—C26109.47 (18)
C16—N11—O12115.83 (18)O21—C21—C211107.29 (19)
C26—N21—O22115.51 (18)C26—C21—C211111.33 (19)
O11—C11—C12106.75 (17)O21—C21—C22109.0 (2)
O11—C11—C16106.83 (17)C26—C21—C22107.37 (19)
C12—C11—C16108.61 (18)C211—C21—C22112.3 (2)
O11—C11—C111110.26 (17)C23—C22—C21110.9 (2)
C12—C11—C111109.65 (19)C23—C22—H22A109.4
C16—C11—C111114.42 (18)C21—C22—H22A109.4
C11—C12—C13112.67 (19)C23—C22—H22B109.4
C11—C12—H12A109.1C21—C22—H22B109.4
C13—C12—H12A109.1H22A—C22—H22B108.0
C11—C12—H12B109.1C24—C23—C22114.8 (2)
C13—C12—H12B109.1C24—C23—H23A108.6
H12A—C12—H12B107.8C22—C23—H23A108.6
C14—C13—C12113.79 (19)C24—C23—H23B108.6
C14—C13—H13A108.8C22—C23—H23B108.6
C12—C13—H13A108.8H23A—C23—H23B107.5
C14—C13—H13B108.8C25—C24—C27118.3 (3)
C12—C13—H13B108.8C25—C24—C23122.4 (2)
H13A—C13—H13B107.7C27—C24—C23119.4 (2)
C17—C14—C15119.3 (2)C210—C25—C24119.8 (2)
C17—C14—C13118.0 (2)C210—C25—C26122.2 (2)
C15—C14—C13122.6 (2)C24—C25—C26117.9 (2)
C14—C15—C110118.4 (2)N21—C26—C25129.7 (2)
C14—C15—C16118.9 (2)N21—C26—C21113.56 (19)
C110—C15—C16122.7 (2)C25—C26—C21116.7 (2)
N11—C16—C15128.9 (2)C28—C27—C24121.5 (3)
N11—C16—C11113.4 (2)C28—C27—H27119.2
C15—C16—C11117.60 (19)C24—C27—H27119.2
C18—C17—C14121.3 (3)C27—C28—C29120.0 (2)
C18—C17—H17119.3C27—C28—H28120.0
C14—C17—H17119.3C29—C28—H28120.0
C19—C18—C17119.6 (2)C210—C29—C28119.8 (3)
C19—C18—H18120.2C210—C29—H29120.1
C17—C18—H18120.2C28—C29—H29120.1
C110—C19—C18120.4 (3)C25—C210—C29120.6 (2)
C110—C19—H19119.8C25—C210—H210119.7
C18—C19—H19119.8C29—C210—H210119.7
C19—C110—C15120.9 (3)C21—C211—H21A109.5
C19—C110—H110119.5C21—C211—H21B109.5
C15—C110—H110119.5H21A—C211—H21B109.5
C11—C111—H11A109.5C21—C211—H21C109.5
C11—C111—H11B109.5H21A—C211—H21C109.5
H11A—C111—H11B109.5H21B—C211—H21C109.5
O11—C11—C12—C1357.8 (2)O21—C21—C22—C23179.7 (2)
C16—C11—C12—C1357.1 (2)C26—C21—C22—C2361.1 (3)
C111—C11—C12—C13177.22 (18)C211—C21—C22—C2361.6 (3)
C11—C12—C13—C1445.0 (3)C21—C22—C23—C2439.2 (3)
C12—C13—C14—C17163.5 (2)C22—C23—C24—C256.6 (3)
C12—C13—C14—C1518.8 (3)C22—C23—C24—C27174.6 (2)
C17—C14—C15—C1103.8 (3)C27—C24—C25—C2100.8 (3)
C13—C14—C15—C110173.9 (2)C23—C24—C25—C210179.7 (2)
C17—C14—C15—C16176.0 (2)C27—C24—C25—C26176.2 (2)
C13—C14—C15—C166.3 (3)C23—C24—C25—C262.6 (3)
O12—N11—C16—C152.6 (3)O22—N21—C26—C251.0 (4)
O12—N11—C16—C11179.40 (17)O22—N21—C26—C21176.56 (18)
C14—C15—C16—N11156.4 (2)C210—C25—C26—N2127.7 (4)
C110—C15—C16—N1123.4 (4)C24—C25—C26—N21155.3 (2)
C14—C15—C16—C1120.4 (3)C210—C25—C26—C21154.8 (2)
C110—C15—C16—C11159.9 (2)C24—C25—C26—C2122.2 (3)
O11—C11—C16—N11113.0 (2)O21—C21—C26—N215.8 (3)
C12—C11—C16—N11132.2 (2)C211—C21—C26—N21112.7 (2)
C111—C11—C16—N119.3 (3)C22—C21—C26—N21124.0 (2)
O11—C11—C16—C1569.8 (2)O21—C21—C26—C25172.07 (19)
C12—C11—C16—C1545.0 (3)C211—C21—C26—C2569.5 (3)
C111—C11—C16—C15167.9 (2)C22—C21—C26—C2553.8 (3)
C15—C14—C17—C181.6 (3)C25—C24—C27—C280.2 (4)
C13—C14—C17—C18176.2 (2)C23—C24—C27—C28179.1 (2)
C14—C17—C18—C191.1 (4)C24—C27—C28—C290.5 (4)
C17—C18—C19—C1101.6 (4)C27—C28—C29—C2100.7 (4)
C18—C19—C110—C150.6 (4)C24—C25—C210—C290.7 (4)
C14—C15—C110—C193.3 (4)C26—C25—C210—C29176.3 (2)
C16—C15—C110—C19176.4 (2)C28—C29—C210—C250.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O11—H11···O210.911.832.725 (2)165
O12—H12···N11i0.892.012.801 (3)147
O21—H21···N210.802.002.505 (2)121
O22—H22···O11ii0.911.762.670 (2)176
C211—H21C···O22iii0.982.583.474 (3)151
C110—H110···O120.952.202.753 (3)116
C210—H210···O220.952.252.796 (3)116
Symmetry codes: (i) x, y+2, z; (ii) x1, y, z; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC11H13NO2
Mr191.22
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)7.3655 (2), 9.6851 (2), 14.4720 (1)
α, β, γ (°)93.375 (1), 99.476 (1), 102.288 (1)
V3)990.22 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.46 × 0.11 × 0.01
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2002)
Tmin, Tmax0.960, 0.999
No. of measured, independent and
observed [I > 2σ(I)] reflections
11309, 3654, 2215
Rint0.068
(sin θ/λ)max1)0.605
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.121, 0.99
No. of reflections3654
No. of parameters266
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.22

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT (Siemens, 1995) and SADABS (Sheldrick, 2002), SHELXTL (Bruker, 2001), SHELXTL, DIAMOND (Brandenburg, 2005).

Selected geometric parameters (Å, º) top
O11—C111.448 (2)N11—C161.288 (3)
O12—N111.403 (2)N21—C261.278 (3)
O21—C211.436 (3)C11—C1111.516 (3)
O22—N211.392 (2)C21—C2111.521 (3)
O11—C11—C12—C1357.8 (2)C211—C21—C22—C2361.6 (3)
C111—C11—C12—C13177.22 (18)C23—C24—C25—C210179.7 (2)
O12—N11—C16—C11179.40 (17)O22—N21—C26—C21176.56 (18)
Zero-point energy ZPE(B3LYP/6–31G**) corrected relative energies (kcal mol−1) of the three conformers discussed and two transition states top
method/basisOH–eqiOH–axskewTS1TS2
(a)0.01.931.022.123.58
(b)0.02.251.312.313.82
(c)0.01.730.921.973.41
(d)0.01.500.392.263.72
(e)0.01.210.302.523.31
(i) The absolute energies for the OH–equatorial conformer for the methods listed are −632.169233, −631.399926, −632.196664, −630.278978 and −630.321458.

(a) B3LYP/6–31G**; (b) PBEPBE/6–31G**; (c) SP B3LYP/6–31+G**//B3LYP/6–31G**; (d) MP2/6–31G**; (e) SP MP2/6–31+G**//MP2/6–31G**.;
Hydrogen-bonding geometry (Å, °) for (IIb) and results of density functional theory (DFT) calculations top
NotationD—-H···AD—-HH···AD···AD—-H···A
aO11—H11···O210.911.832.725 (2)165
DFT0.901.532.429173
bO22—H22···O11ii0.911.762.670 (2)176
DFT1.051.662.661157
cO12—H12···N11i0.892.012.801 (3)147
DFT0.962.0632.726143
dO21—H21···N210.802.002.505 (2)121
DFT1.071.632.287114
C211—H21C···O22iii0.982.583.474 (3)151
DFT1.002.6193.452149
C110—H110···O120.952.202.753 (3)116
DFT1.042.362.776102
C210—H210···O220.952.252.796 (3)116
DFT1.022.4752.996114
Symmetry codes: (i) − x, − y + 2, − z; (ii) x − 1, y, z; (iii) x + 1, y, z;
 

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